200415155 ⑴ 玖、發明說明 【發明所觸之技術領域】 木發明係關於透明嵌段共聚物，特別係關於由經胃& 烯丛取代的芳族單體和共軛二烯製得的透明嵌段共聚牧j。 本發明亦係關於製造透明嵌段共聚物之方法，特別係_於^ 向經喂乙烯基取代的芳族單體和共軛二烯製造透明嵌.段# 聚物之方法。 【先前技術】 EP-A-02705 1 5和其相關的 US-A-493 92 0 8提出以式200415155 玖 发明, Description of the invention [Technical field touched by the invention] Wood invention is about transparent block copolymers, especially about transparent embedded copolymers made of aromatic monomers and conjugated diene substituted by stomach & Duan Gongmu j. The present invention also relates to a method for manufacturing a transparent block copolymer, in particular to a method for manufacturing a transparent embedded segment polymer to a vinyl-substituted aromatic monomer and a conjugated diene. [Prior art] EP-A-02705 1 5 and its related US-A-493 92 0 8
Si-Bi-B/S-S2表不之具有兩個分子量不同之經單乙燦基取 代的芳族嵌段S!和S2的透明直鏈嵌段共聚物之製備。胃 別地，其提出耐衝擊性獲改善之透明直鏈樹脂共軛二锦/ 經單乙烯基取代的芳族嵌段共聚物。 雖然如此，如此技術已知者，直鏈結構有時難加工， 在局切剪模塑系統（如：注模或吹膜壓出）中特別是如此。 具有至少三個支鏈和具多形態結構的樹脂嵌段共聚物述於 Moczygemba 等人的美國專利案第 5,705,5 69 號。 Moczygemba等人所提出的方法，基於雙重引發，不易良 好控制分子量。A h m e d等人於美國專利案第6，1 2 7 5 4 8 7號 中試圖要改善透明嵌段共聚物的性質均衡。發展用以製造 Ahmed產物的此方法因爲須要至少12個步驟才能自其溶 劑回收共聚物，所以其工業用途低。Trepka等人的美國 專利案第6,26 5，4 8 5號提出樹脂組成遞變的嵌段共聚物， (2) (2)200415155 其爲淡藍色並具良好衝擊強度。如高衝擊性質常見者， Trepka之共聚物的澄淸度顯然受到方法中所用組成遞變 順序的影響。 因此’此技術對於光學和機械性質具進一步改善組合 者有需求存在，特別是透明度和耐衝擊度皆高且加工性高 (特別是流動性高）的樹脂，此使得材料比以前者的應用更 寬廣，也可以藉比以前者之範圍來得廣的模塑技巧（特別 是加壓、板或膜壓出和注射模塑）製造。簡言之，對於旋 流率高（顯示良好可加工性）、彎曲模量高（顯示剛性）、破 裂時拉伸率高（顯示彈性）、耐衝擊性高（顯示柔軟性）和濁 度低（顯示透光性）之經改良的聚合物有需求存在。 本發明針對符合前述段落提出的這些需求。 此技術也已經知道形成高強度合成橡膠（如··聚丁二 _)和聚苯乙烯、選用的一或多種嵌段共聚物（.如：苯乙 烯-丁二烯-苯乙烯嵌段共聚物）之摻合物（例如，4 〇重量。/〇 本乙綠和選用的高衝擊聚苯乙烯（如：0 · 2 5至2重量％))， 而製得耐衝擊性高的透明嵌段共聚物。但這些摻合物展現 的性質不及所需；例如，這些摻合物因爲苯乙烯含量低而 使得透光度低。 本發明亦針對克服以前技術的這些問題。 【發明內容】 本發明提出一種新穎之經單乙烯基取代的芳族烴和共 軛二烯的透明樹脂嵌段共聚物’其於物件的轉變期間內之 -5- (3) (3)200415155 加工性佳且耐衝擊性高，彎曲模量高且透光度高。 本發明的另一目的是要提出一種新穎之經單乙烯基取 代的芳族烴和共軛二烯的透明樹脂嵌段共聚物，其適用於 與苯乙嫌聚合物摻合，該摻合物的耐衝擊性高、彎曲模量 高、透光率高且在物件轉變期間內的加工性高。 本發明亦提出一種製造本發明之透明樹脂共聚物之方 法。 因此，本發明提出一種製造如申請專利範圍第1至7 項中定義之透明樹脂共聚物之方法。本發明亦提出可藉本 β 發明之方法得到的聚合物。 本發明亦提出如申請專利範圍第1至9至1 5項中定 義之共聚物。 本發明亦提出一種樹脂摻合物，包含至少一種本發明 之透明樹脂共聚物。本發明最後提出製造模塑物件之方法 ，其包含注射本發明之透明樹脂共聚物或摻合物的步驟。 【實施方式】 Φ 共聚物 基於本發明者之發現而完成本發明，用以製造透明樹 脂共軛二烯/經單乙烯基取代的芳族嵌段共聚物時，最感 興趣的是使用的方法中，先以多官能性鈍化劑至少部分鈍 化具活性的共聚物種1^31-：81-]\4(其中1是經單乙烯基取 代的芳族均聚物，Β】是共軛二烯均聚物，Μ是鹼金屬、R 是烷基（RM是引發劑）），該產製包含使用單官能性鈍化劑 -6 - (4) (4)200415155 (終結劑）進行至少具活性的組成遞變嵌段共聚物種R-S , -(將進料B2/S2加至反應介質中而得）的第二次 全體鈍化，至少兩種於原處製得的聚合物種存在，得到光 學和機械性的良好組合及改良的流動性質。 控制乙烯基芳族含量，兩種主要物種的分子量及它們 的相對比例，以達到最終機械性質和經改良的可加工性。 兩種主要物種的相對比例正比於多官能性鈍化劑與活性引 發劑的莫耳比（相對於化學計量比）。如前述者，因此，本 發明之方法大多基於此比例之控制，以選定的單體相對含 量，達到樹脂共聚物的最終性質。 因此，如果第一種聚合物種（S^BQX是，如：苯乙烯 含量高（如：超過50重量％)的苯乙烯—丁二烯嵌段共聚物 ，而第二種嵌段聚合物種的苯乙烯含量高（如：超過8 0重 量％)，此可提供嵌段共聚物高透光度和高衝擊強度。原處 生成的第一和第二種聚合物種提供可加工度高的聚合物等 級，其可便於在壓出管線、注射機械、吹膜管線或吹塑管 線中流動。應注意到’此方法可於多個反應器中進行，之 後混合所得聚合物溶液。 在製造多重嵌段透明共軛二烯/經單乙烯基取代的芳 族嵌段共聚物之不同嵌段或鏈段並控制不同嵌段的比例時 ，施用連續或逐步聚合反應，在所得嵌段共聚物性質方面 獲致意料之外和令人訝異的效果，本發明者基於此發現而 完成本發明。 最特別地’已經發現到，獲得經改善的耐衝擊性的同 -7- (5) (5)200415155 時，聚合物濁度會降低，這是因爲橡膠相於高苯乙烯基質 中達較佳分散，藉此有助於聚合物的透光度之故。據此， 這樣的已知嵌段共聚物中之妥協存在，根據本發明，可以 去除耐衝擊性和濁度性質之間的對立狀態。據此，根據本 發明製得的透明嵌段共聚物可用於須要高透光度和耐衝擊 性的新應用，目前有其他聚合物（如：聚丙烯和聚對苯二 甲酸乙二酯）符合這樣的性質。 此外，根據本發明製得的嵌段共聚物具高流動性，例 如，藉聚合物旋流率測得，有助於聚合物藉壓縮、壓出或 注射模塑加工。 >較佳情況中，存在於本發明之嵌段聚合物種中之共軛 二烯和經單乙烯基取代的芳族單體之間的重量比介於約 1 5 : 8 5和3 0 : 7 0之間，約15 : 8 5至約3 5 : 7 5更佳。使 用超過8 5份經單乙烯基取代的芳族單體時，耐衝擊強度 和拉伸率降低，而使用低於7 0份經單乙烯基取代的芳族 單體時，聚合物具彈性質地且所須性質受損。最佳情況中 ，嵌段共聚物的苯乙烯和二烯比由7 5 : 2 5至82 : 18，更 常是約8 0 : 2 0。 本發明之嵌段共聚物的苯乙烯總含量對嵌段共聚物的 耐衝擊性影響顯著。連續提高苯乙烯含量幾乎持續改善聚 合物的光學性質，此不適用於耐衝擊性，於選定苯乙烯含 量，耐衝擊性迅速降低。 另基於本發明者發現到，透明嵌段共聚物的耐衝擊性 受到經單乙烯基取代的芳族單體（如：苯乙烯）含量和經單 (6) (6)200415155 乙烯基取代的芳族單體於第一和第二種聚合物種中之分佈 之影響。經單乙烯基取代的芳族單體（如：苯乙烯）於共軛 二烯鏈中之分佈導致形成組成遞變嵌段，將此稱爲-B 2 / S 2 -鏈段。在組成遞變嵌段中，單體序列分佈可以描述成第一 個嵌段部分（其富含二烯），之後是中間嵌段部分（其初時 富含二烯，組成逐漸改變直到變成富含經單乙烯基取代的 芳族單體）和經單乙烯基取代的芳族單體的最終嵌段。更 完整描述見方< H.L.Hsieh and R.P.Quirk, "Anionic polymerisation (陰離子聚合反應），，，Marcel Dekker Inc. (1 9 9 6 )。必須注意到經單乙烯基取代的芳族單體於共軛二 烯/經單乙烯基取代的芳族共聚物中之分佈不規則性。經 單乙烯基取代的芳族單體的不規則性或不規則化以達到最 低初値1 〇 %爲佳。經單乙烯基取代的芳族單體或無規苯乙 烯的”不規則性”或’’不規則化”定義爲受束縛之經單乙烯基 取代的方族煙總含量減去經單乙烯基取代的芳族烴總含量 之間的差値，此二種含量皆以相對於樹脂總重％表示。嵌 段和經單乙燃基取代的芳族烴總含量係使用Nmr技巧測 得。例如，不規則性由1 5至2〇%。 根據本發月的f寸點’根據本發明製得的組成物包含下 列聚合物種； (i) R- ( S ] -B ] )χ (11) R - S ] - Β ] - β 2 / s 2 · Μ 一中主女物種（])和（η)以高濃度存在於反應介質中，物種 (7) (7)200415155 (i)是短鏈，其分子量低於物種（ii)的長鏈或直鏈結構。 活性物種（ii)經終端劑處理，以回收鈍化的聚合物。（ 因爲溶劑中有雜質和/或淸除劑（K終結者）、單體進料和 鈍化劑存在，非常少量的活性聚合物種R- S , -M和/或活 性聚合物種R-S^B^M被鈍化，分別形成聚合物種（iii)R-S^K-M和聚合物種（iAOR-S^B^K-M。就本發明之目的， 可以忽略這些物種）。 偶合之類的共聚物，即，第一種共聚物種（i)，可以是 各種類型；其亦可具無規本質。一般可稱爲、 (Si-S2-Bi)n、(8】-82/8】)!！..等 0 直鏈無規共聚物種（ii)亦可爲各式各樣類型。例如， 其可爲 SrBrS/B:、S】-B】-S2/B】-S3.·等。這樣的結構例 見於前述專利案 EP-A-02 705 1 5、US-P-5 7 05 5 69、US-P-6]27487 和 US-P-6265485 ° 根據本發明之特點，S 1和S2是經單乙烯基取代的芳 族均聚物嵌段，S!分子量約5 000道耳呑至20000道耳呑 ，S 2約5 0 0 0 0道耳吞至約1 5 0 0 0 0道耳呑。B !是共$尼二烯 均聚物嵌段，其分子量約3 0 0 0道耳吞至1 0 0 0 0道耳呑。 B2/S2是共轭二烯/經單乙烯基取代的芳族無規共聚物嵌 段（組成遞變嵌段），其分子量約10000道耳吞至約1 00000 道耳吞。S2分子量遠大於S]，例如5局至30倍。 根據本發明之方法得到的共聚物種（i i)之分子量通常 由約100000道耳呑至約300000道耳呑，以由約140000 道耳吞至200000道耳呑爲佳，特別是由約150000道耳吞 (8) (8)200415155 至約1 8 0 0 0 0道耳呑。 較佳情況中，共聚物種（i)包含約40至60重量％共軛 二烯單元和約60至40重量％經單乙烯基取代的芳族單元 〇 較佳情況中，此透明嵌段共聚物種（i i)含有約1 5至 4 0重量％共軛二烯單元和約6 0至8 5重量％經單乙烯基取 代的芳族單元。 溶劑蒸發之後回收的最終透明嵌段共聚物在甲苯中之 黏度由2至lOcst (於25°C，使用聚合物於甲苯中的5.23 重量％溶液測得），熔流指數（MI 5 /2 0 0 °C )由 1 至 4 0 g /1 0 0 mi η，以5至2 5 g /1 0 m i η爲佳，熔流指數Μ I係根 據ASTM的方法，使用200°C和5kg重量測得。溶劑蒸發 之後回收的最終透明嵌段共聚物含有5重量％至40重S %. 共聚物種（i)。 用於本發明的共軛二烯例包括1，3·丁二烯、異 烯、戊間二烯、2,3-二甲基-1,3-丁二烯、3-丁基_】，3 —辛一 烯、2-苯基-1,3-丁二烯及它們的混合物。 /[> ώ^η ^ 可用於本發明之嵌段共聚物之經單乙烯基取& ~ 單體包括，如··苯乙烯、α -甲基苯乙烯、乙燏_甲~ 4-正丙基苯乙烯、4-環己基苯乙烯、扣癸基苯乙輝' 求基_間_ 基-4-苯甲基-苯乙烯、4-對-甲苯基苯乙烯、4-([本资 ^ 因1爲 丁基）苯乙烯、乙烯基-萘和環經取代的其他苯乙体° 十/姨和 可利用性和穩定的良好結果，所以苯乙烯、異間戊/ 1,3-丁二烯是較佳單體。 -11 - 200415155 Ο) 通常，在此技術中，共軛二烯和經單乙烯基取代的芳 族單體以沒有雜質地作爲反應介質中之淸除劑爲佳。 方法 可於引發劑存在下，在溶劑介質中，藉陰離子嵌段聚 合反應製得此透明嵌段共聚物。下列揭示者係參考本發明 之方法的一個較佳實施例，但嫻於此技術者知道此可以有 變化並用於任何方法。 聚合反應於惰性氣體（如：氮）下，於溶劑中進行，以 無氧和水爲佳。有引發劑存在下進行聚合反應。可用於本 發明的適當引發劑例見於Lanza等人的美國專利案第 4，93 9 ;2 08號。通常，引發劑是式RM的有機鹼金屬化合 物，其中R是具，如：4至8個碳原子的烷基、環烷基或 芳基，Μ是鹼金屬。較佳引發劑是有機鋰化合物，如：乙 基鋰、丙基鋰、丁基鋰、戊基鋰、己基鋰、環己基鋰、苯 基鋰、甲苯基鋰、萘基鋰和它們的異構物，特別是第二丁 基鋰、正丁基鋰和第三丁基鋰。 本發明之聚合法中所用的該引發劑量視所欲分子量而 定。所用引發劑較少時，活性位址較少，添加單體時，單 體與較少的活性位址反應，分子量提高。 可用於本發明的適當溶劑量可見於Lanza等人的美國 專利案第4,93 9,208號。此溶劑可爲脂族、脂環族或芳族 烴（引發劑通常是有機鋰化合物）。可用於本發明之聚合法 的適當溶劑例包括芳族烴（如：苯、甲苯、二甲苯、乙苯 (10) (10)200415155 和萘）及脂族和環脂族烴（如：異丁烷、正戊烷、環戊烷、 己烷、環己烷、甲基環己烷）和它們的混合物。環己烷（以 環己烷和己烷之混合物爲佳）是較喜用者，這是因爲它們 的可利用性和使用富含苯乙烯的聚合系統時，其於苯乙烯 中之溶解度之故。 溶劑與引至反應介質中之單體總進料之間的重量比視 介質黏度和在反應器中的熱轉移量而定，但以介於約2 : 1和1 〇 : 1之間爲佳，介於約3 : 1和6 : 1之間最佳。 溶劑中的雜質（如：水、醇、硫醇之類）會損及引發劑 和/或活性鏈，以根據此技術中已知技巧移除爲佳。 根據本發明之聚合反應以於-20 °C至150 °C、壓力足 以使單體和溶劑維:持液相的條件下實行爲佳。更佳情況中 ，聚合反應的實施溫度介於約2 0 °C和1 2 0 °C之間，壓力介 於大氣壓和1 0巴之間。根據本發明的一個實施例，控制 均聚反應和共聚反應階段期間內的各步驟的各溫度；這樣 的控制可藉此技術中描述之任何已知冷卻系統（如：使用 迴餾冷卻器、具循環幫浦的外部熱交換機之類）達成。 根據本發明的一個特點，此發明之方法包含將四種單 體（分别是S】、B】、B 2、S 2)分別以Q s】、Q b !、Q b 2、Q s 2 量引入或供應至反應器。此方法中，單體進料的個別量是 Qh、Qb]、Qb2、Qs2，總單體進料量以Qm表示。 根據本發明的此實施例之方法主要包含四個步驟。 步驟（1 )是在足量有機鹼金屬引發劑RM存在以引發 聚合反應及達到所欲分子量之時，將溶劑（以極性化合物 -13- (11) (11)200415155 爲佳，請參考下文）和經單乙烯基取代的芳族單體（sι)引至 反應器中，以形成第一種嵌段物種R-S^M。藉連線或實 驗室凝膠渗透層析術（G P C )控制分子量。s ]與總單體進料 的重量比介於5 %和3 0 %之間，1 0 %至2 5 % (含）最佳。 此步驟之初，在溶劑和有機鋰引發劑存在下，經單乙 烯基取代的芳族單體溫度（稱爲引發溫度Tinit)以設定低於 6〇°C爲佳，低於55°C較佳。 步驟（1 )的接觸時間足以發生聚合反應直到基本上所 有單體耗盡。可由溫度情況（出現高溫）或連線光譜術追蹤 聚合反應完成與否。 爲提高引發和傳播速率，特別是使用烷基鋰（如：正 丁基鋰）時，可添加少量極性化合物，在添加引發劑之前 ’極性化合物與溶劑之混合物加入反應介質中.。藉由修飾 介質極性，能夠在混合物中的該單體與共軛二烯之共聚反 應期間內’影響經單乙烯基取代的芳族單體的不規則分佈 〇 步驟（2)是將步驟（1)之後得到的活性膠結材料引至共 軛二烯單體（B 〇中。Β ι與單體總進料的重量比以介於2 % 和2 0%之間爲佳，介於5%和15%之間最佳。步驟（2)的接 觸時間足以使反應發生至基本上所有的單體耗盡爲止。 步驟（3)是在步驟（2)完成之後，引入多官能性鈍化劑 X。此技術中已知的此鈍化劑是偶合劑，但此處用於不同 用途，其部分消除或鈍化。下文中，將其稱爲鈍化劑或偶 合劑（之間無差別）。選擇該多官能性鈍化劑的r量，以低 (12) (12)200415155 於相對於實際用以引發聚合反應的引發劑量（RMa)之計量 比。 本發明的關鍵之一是控制引發劑的鈍化劑的個別量。 依活性引發劑莫耳量RM a調整r量，使得活性聚合物鏈僅 部分被鈍化。例如，僅60%活性聚合物鏈被多官能性鈍化 劑所鈍化。多官能性鈍化劑X基本上有n個官能性（n由2 至8，以大於2爲佳）’該η能夠鈍化η個活性聚合物種 ，鈍化劑加至反應介質中，根據本發明的關鍵之一，其添 加量視活性引發劑量而定。 Φ 本發明中，鈍化劑X :引發劑（如：RMa)的化學計量 比介於〇 · 5和0.9之間，以介於〇 . 6和0.8之間爲佳。 此比例與引入的多官能性鈍化劑和活性引發劑的莫耳 量可控制短鏈/長鏈比及它們的個別分子量。 適當鈍化劑是US-P- 5,5 4 5,6 9 0第3和4欄中所列偶 合劑。例子有二或多乙烯基芳族化合物、二或多酮、二或 多鹵化物（以鹵化矽或鹵矽烷爲佳）、一醇與多羧酸的酯類 之類及二或多種化合物之混合物。較佳類型是環氧化的植 鲁 物油（如：環氧化的大豆油、環氧化的蓖麻油之類）或它們 的混合物（如：Flexol Plasticizer LOE (DOW)或 Edenol B316(Henkel)或 Vikoflex® (Dow)) 〇 步驟（4 )是引入共軛一燃（B 2)和經單乙烯基取代的芳族 物（S2)之混合物。此反應通常於不規則劑或不規則分佈劑 存在下進行。 將不規則分佈劑引至存在於反應介質中的溶劑中，確 -15- (13) (13)200415155 保B2/s2鏈段中的單體不規則分佈。此不規則分佈劑是極 性化合物，選自路易士鹼（如：三級胺）和極性劑（包含醚（ 包括環狀醚、脂族一醚和脂族多醚））。其他物劑包括，如 :三乙胺、三丙胺、三丁胺、N-二甲基苯胺、四甲基乙 二胺、吡啶、晴啉和三甲基乙二胺（此爲三級胺的例子）。 這樣的物劑的醚的例子中，此物劑可包括四氫呋喃、C2 和C3二烷基醚、二乙二醇二甲醚、二乙二醇二乙醚、茴 香醚、二噁j：完、1，2 -二甲氧基乙院和四氫吡喃。不規則分 佈劑（特別是極性劑）用量可以是0 ·0 1至5份/ 1 0 0重量份 樹脂（phi·)。 適當選擇極性化合物或不規則劑’能夠調整分散於共 軛二烯相中，之不規則經單乙烯基取代的芳族單體之比例。 這些極性化合物也會影響共軛二烯單體的1，2加成反應和 所得乙烯基特性，所以可調整共聚物的Bl-B2/S2部分的分 子結構。 本發明的一個實施例中，可以便利地添加額外量的不 規則劑或極性化合物或它們的混合物，以提高經單乙烯基 取代的芳族單體的不規則部分和/或促進共軛一烯的]，2 _ 加成反應。 S 2與單體總進料的重量比介於5 0 %和8 0 %之間’介於 55%和70%之間最佳。I與總單體進料之間的重量比介於 5 %和2 5 %之間，介於7 %和2 0 %之間最丨土。 該步驟（4)開始時，反應介質溫度（共聚反應溫度，Si-Bi-B / S-S2 represents the preparation of a transparent straight-chain block copolymer having two monoethylenyl-substituted aromatic blocks S! And S2 having different molecular weights. In addition, it proposes a transparent linear resin conjugated dibasic / monovinyl-substituted aromatic block copolymer with improved impact resistance. Nonetheless, as is known in the art, linear structures are sometimes difficult to process, especially in partial-cut shear molding systems such as injection molding or blown film extrusion. A resin block copolymer having at least three branches and having a polymorphic structure is described in U.S. Patent No. 5,705,5 69 to Moczygemba et al. The method proposed by Moczygemba et al. Is based on dual initiation and it is not easy to control molecular weight well. Ahmed et al. In U.S. Patent No. 6, 1 2 7 5 4 8 7 sought to improve the balance of properties of transparent block copolymers. This method developed to produce Ahmed products has low industrial use because it requires at least 12 steps to recover the copolymer from its solvent. Trepka et al., U.S. Patent No. 6,26 5,4 8 5 proposes a block copolymer with a gradually changing resin composition. (2) (2) 200415155 is light blue and has good impact strength. As is common with high-impact properties, the clarity of Trepka's copolymers is clearly affected by the order of the compositional gradients used in the method. Therefore, 'this technology has a demand for those who have further improved optical and mechanical properties, especially resins with high transparency and impact resistance and high processability (especially high fluidity), which makes the material more useful than the former. It is also broad and can be manufactured by a wider range of molding techniques (especially compression, plate or film extrusion and injection molding) than the former. In short, for high swirl rates (showing good workability), high flexural modulus (showing rigidity), high elongation at break (showing elasticity), high impact resistance (showing flexibility), and low turbidity There is a need for improved polymers (showing light transmission). The present invention addresses these needs as set forth in the preceding paragraphs. This technology is also known to form high-strength synthetic rubber (such as polybutadiene) and polystyrene, and one or more block copolymers (such as: styrene-butadiene-styrene block copolymers). ) Blends (for example, 40 wt./benz green and selected high-impact polystyrene (eg, 0.25 to 2 wt%)) to obtain transparent blocks with high impact resistance Copolymer. However, these blends exhibit less desirable properties; for example, these blends have low light transmission due to low styrene content. The present invention also aims to overcome these problems of the prior art. [Summary of the Invention] The present invention proposes a novel monovinyl-substituted aromatic hydrocarbon and conjugated diene-based transparent resin block copolymer 'within the transition period of the object -5- (3) (3) 200415155 Good processability, high impact resistance, high flexural modulus and high light transmittance. Another object of the present invention is to propose a novel monovinyl-substituted aromatic hydrocarbon and conjugated diene transparent resin block copolymer, which is suitable for blending with styrene polymers, and the blend Has high impact resistance, high flexural modulus, high light transmittance, and high processability during object transformation. The present invention also proposes a method for manufacturing the transparent resin copolymer of the present invention. Therefore, the present invention proposes a method for manufacturing a transparent resin copolymer as defined in claims 1 to 7 of the scope of the patent application. The invention also proposes polymers obtainable by the method of the beta invention. The present invention also proposes copolymers as defined in claims 1 to 9 to 15 of the scope of the patent application. The invention also provides a resin blend comprising at least one transparent resin copolymer of the invention. The present invention finally proposes a method for manufacturing a molded article, which comprises the step of injecting the transparent resin copolymer or blend of the present invention. [Embodiment] The Φ copolymer is based on the discovery of the present inventors and completed the present invention. When manufacturing a transparent resin conjugated diene / monovinyl substituted aromatic block copolymer, the method of most interest is the method used. In the first, a polyfunctional passivating agent is used to at least partially passivate the active copolymer 1 ^ 31-: 81-] \ 4 (where 1 is a monovinyl substituted aromatic homopolymer, B] is a conjugated diene Homopolymer, where M is an alkali metal and R is an alkyl group (RM is an initiator)) The production process includes the use of a monofunctional passivator-6-(4) (4) 200415155 (terminator) for at least active Composition tapered block copolymer species RS,-(obtained by adding feed B2 / S2 to the reaction medium) the second overall passivation, at least two polymer species prepared in situ exist, obtaining optical and mechanical properties Good combination and improved flow properties. The vinyl aromatic content, the molecular weights of the two major species, and their relative proportions are controlled to achieve final mechanical properties and improved processability. The relative proportion of the two main species is proportional to the molar ratio (relative to stoichiometric ratio) of the multifunctional passivating agent and the active initiator. As mentioned above, therefore, the methods of the present invention are mostly based on the control of this ratio, with the relative content of the selected monomers to achieve the final properties of the resin copolymer. Therefore, if the first polymer species (S ^ BQX is, for example, a styrene-butadiene block copolymer with a high styrene content (eg, more than 50% by weight), and the benzene of the second block polymer species High ethylene content (eg, more than 80% by weight), which provides high light transmittance and high impact strength of the block copolymer. The first and second polymer species generated in situ provide polymer grades with high processability It can be easily flowed in the extrusion line, injection machinery, blown film line or blown line. It should be noted that 'this method can be performed in multiple reactors and the resulting polymer solution is mixed afterwards. In the manufacture of multi-block transparency When different blocks or segments of conjugated diene / monovinyl substituted aromatic block copolymers are controlled and the proportion of different blocks is controlled, continuous or stepwise polymerization is applied, and the properties of the obtained block copolymer are unexpected. In addition to the surprising and surprising effects, the present inventors have completed the present invention based on this finding. Most particularly, 'it has been found that when the improved impact resistance is obtained, it is the same as -7- (5) (5) 200415155, Polymer turbidity decreases, which Because the rubber phase is better dispersed in the high styrene matrix, thereby contributing to the transparency of the polymer. Accordingly, compromises exist in such known block copolymers, which can be removed according to the present invention The opposite state between impact resistance and turbidity properties. According to this, the transparent block copolymer prepared according to the present invention can be used for new applications that require high light transmittance and impact resistance. At present, there are other polymers (such as: Polypropylene and polyethylene terephthalate) meet such properties. In addition, the block copolymers prepared according to the present invention have high fluidity, which, for example, is measured by the polymer's swirl rate, which helps the polymer Processed by compression, extrusion, or injection molding. ≫ Preferably, the weight ratio between the conjugated diene and the monovinyl-substituted aromatic monomer present in the block polymer species of the present invention is Between about 15: 8 5 and 30: 70, more preferably between about 15: 85 and about 35: 75. Impact resistance when using more than 85 parts of monovinyl-substituted aromatic monomers Reduced strength and elongation while using less than 70 parts of monovinyl substituted aromatic monomer The polymer has an elastic texture and the required properties are impaired. In the best case, the styrene and diene ratio of the block copolymer ranges from 7 5: 25 to 82: 18, and more often about 80: 20. The total styrene content of the block copolymer of the present invention has a significant impact on the impact resistance of the block copolymer. Continuously increasing the styrene content almost continuously improves the optical properties of the polymer. This is not suitable for impact resistance. Content, impact resistance decreases rapidly. Also based on the inventors' discovery, the impact resistance of transparent block copolymers is affected by the content of aromatic monomers (such as styrene) substituted by monovinyl and by (6) ( 6) 200415155 The effect of the distribution of vinyl-substituted aromatic monomers in the first and second polymer species. Monovinyl-substituted aromatic monomers (such as styrene) in the conjugated diene chain The distribution results in the formation of a tapered compositional block, which is referred to as the -B 2 / S 2-segment. In the compositionally tapered block, the monomer sequence distribution can be described as the first block portion (which is rich in diene), followed by the middle block portion (which is initially rich in diene, and the composition gradually changes until it becomes rich). Contains monovinyl substituted aromatic monomers) and the final block of monovinyl substituted aromatic monomers. For a more complete description see H.L. Hsieh and R.P. Quirk, " Anionic polymerisation, ", Marcel Dekker Inc. (19 9 6). It must be noted that the monovinyl-substituted aromatic monomer has irregular distribution in the conjugated diene / monovinyl-substituted aromatic copolymer. It is preferred that the monovinyl-substituted aromatic monomers have irregularities or irregularities to reach a minimum initial value of 10%. "Irregularity" or "randomization" of monovinyl-substituted aromatic monomers or random styrene is defined as the total content of bound, monovinyl-substituted square cigarettes minus monovinyl The difference between the total content of substituted aromatic hydrocarbons, both of which are expressed as% relative to the total weight of the resin. The total content of block and monoethenyl-substituted aromatic hydrocarbons is measured using the Nmr technique. For example The irregularity is from 15 to 20%. According to the f-inch point of the present month, the composition prepared according to the present invention includes the following polymer species; (i) R- (S] -B]) χ (11) R-S]-Β]-β 2 / s 2 · Μ The main female species (]) and (η) are present in the reaction medium at high concentrations. Species (7) (7) 200415155 (i) are short chains , Its molecular weight is lower than that of long chain or straight chain structure of species (ii). Active species (ii) are treated with a terminator to recover a passivated polymer. (Because of impurities and / or scavengers in the solvent (K Terminator ), Monomer feed and passivation agent are present, very small amounts of reactive polymer species R-S, -M and / or reactive polymer species RS ^ B ^ M are passivated to form polymer species, respectively (Iii) RS ^ KM and polymer species (iAOR-S ^ B ^ KM. For the purposes of this invention, these species can be ignored). Copolymers such as couplings, ie, the first copolymer species (i), can be Various types; it can also have a random nature. Generally it can be called, (Si-S2-Bi) n, (8) -82/8])! .. etc. 0 Linear random copolymers (ii) also It can be of various types. For example, it can be SrBrS / B :, S] -B] -S2 / B] -S3 ... etc. Examples of such a structure can be found in the aforementioned patent EP-A-02 705 1 5 , US-P-5 7 05 5 69, US-P-6] 27487 and US-P-6265485 ° According to the characteristics of the present invention, S 1 and S2 are monovinyl substituted aromatic homopolymer blocks, S! Molecular weight is about 5 000 ears to 20000 ears, S 2 is about 50000 ears to about 15 0 0 ears. B! Segment, its molecular weight is about 30000 channels to 100000 channels. B2 / S2 is a conjugated diene / monovinyl substituted aromatic random copolymer block (the composition is tapered Paragraph), with a molecular weight of about 10,000 channels to about 100,000 channels. S2 has a molecular weight much larger than S], for example 5 to 30 times. According to The molecular weight of the copolymer species (ii) obtained by the method of the invention is usually from about 100,000 channels to about 300,000 channels, preferably from about 140,000 channels to 200,000 channels, especially from about 150,000 channels ( 8) (8) 200415155 to about 18 0 0 0 ears. Preferably, the copolymer species (i) comprises about 40 to 60% by weight of a conjugated diene unit and about 60 to 40% by weight of a monovinyl substituted aromatic unit. In a preferred case, the transparent block copolymer type (Ii) Contains about 15 to 40% by weight of a conjugated diene unit and about 60 to 85% by weight of a monovinyl-substituted aromatic unit. The viscosity of the final transparent block copolymer recovered after solvent evaporation in toluene was from 2 to 10 cst (measured at 25 ° C using a 5.23 wt% solution of polymer in toluene), and the melt flow index (MI 5/2 0 0 ° C) from 1 to 40 g / 1 0 0 mi η, preferably 5 to 25 g / 1 0 mi η, the melt flow index M I is measured according to ASTM method using 200 ° C and 5kg weight Got. The final transparent block copolymer recovered after solvent evaporation contained 5 to 40% by weight of S. copolymer species (i). Examples of the conjugated diene used in the present invention include 1,3-butadiene, isoene, pentadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-], 3-octene, 2-phenyl-1,3-butadiene, and mixtures thereof. / [> ^^ ^ ^ can be used in the block copolymer of the present invention via monovinyl group & ~ monomers include, such as · styrene, α-methylstyrene, acetamidine ~ 4- N-propylstyrene, 4-cyclohexylstyrene, decylphenethyl fluorene 'seeking radical_m-yl-4-benzyl-styrene, 4-p-tolylstyrene, 4-([本^ Because 1 is butyl) styrene, vinyl-naphthalene, and other acetophenones substituted by cyclo ° // 姨 and good availability and stability results, so styrene, isoprenyl / 1,3- Butadiene is the preferred monomer. -11-200415155 0) Generally, in this technique, conjugated diene and monovinyl-substituted aromatic monomers are preferably used as scavengers in the reaction medium without impurities. Method The transparent block copolymer can be obtained by anionic block polymerization in the presence of an initiator in a solvent medium. The following disclosure refers to a preferred embodiment of the method of the present invention, but those skilled in the art know that this can be varied and used in any method. The polymerization is carried out in an inert gas (such as nitrogen) in a solvent, preferably oxygen-free and water. Polymerization is carried out in the presence of an initiator. Examples of suitable initiators that can be used in the present invention are found in U.S. Patent No. 4,93 9; 2 08 to Lanza et al. Generally, the initiator is an organic alkali metal compound of formula RM, where R is an alkyl, cycloalkyl or aryl group having, for example, 4 to 8 carbon atoms, and M is an alkali metal. Preferred initiators are organolithium compounds, such as: ethyl lithium, propyl lithium, butyl lithium, pentyl lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, tolyl lithium, naphthyl lithium and their isomers Substances, especially second butyl lithium, n-butyl lithium and third butyl lithium. The amount of the initiator used in the polymerization method of the present invention depends on the desired molecular weight. When less initiator is used, there are fewer active sites, and when monomers are added, the monomers react with fewer active sites and the molecular weight increases. A suitable amount of solvent that can be used in the present invention can be found in U.S. Patent No. 4,93,208 to Lanza et al. This solvent can be an aliphatic, cycloaliphatic or aromatic hydrocarbon (the initiator is usually an organolithium compound). Examples of suitable solvents that can be used in the polymerization method of the present invention include aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene (10) (10) 200415155, and naphthalene) and aliphatic and cycloaliphatic hydrocarbons (e.g., isobutyl Hexane, n-pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane) and mixtures thereof. Cyclohexane (preferably a mixture of cyclohexane and hexane) is preferred because of their availability and their solubility in styrene when using styrene-rich polymerization systems. The weight ratio between the solvent and the total monomer feed introduced into the reaction medium depends on the viscosity of the medium and the amount of heat transfer in the reactor, but is preferably between about 2: 1 and 1 0: 1 It is best to be between about 3: 1 and 6: 1. Impurities in the solvent (such as water, alcohols, thiols, etc.) can damage the initiator and / or living chain and are best removed according to techniques known in the art. The polymerization reaction according to the present invention is preferably carried out under the conditions of -20 ° C to 150 ° C and sufficient pressure to keep the monomers and solvents in a liquid phase. More preferably, the polymerization is carried out at a temperature between about 20 ° C and 120 ° C, and the pressure is between atmospheric pressure and 10 bar. According to an embodiment of the present invention, the temperature of each step during the homopolymerization and copolymerization reaction stages is controlled; such control can be performed by any known cooling system described in the art (such as the use of a recirculation cooler, a Circulation heat exchangers, etc.). According to a feature of the present invention, the method of the present invention includes the amount of four kinds of monomers (S], B], B 2, S 2), respectively, by Q s], Q b!, Q b 2, Q s 2 Introduced or supplied to the reactor. In this method, the individual amounts of monomer feed are Qh, Qb], Qb2, and Qs2, and the total monomer feed is represented by Qm. The method according to this embodiment of the present invention mainly includes four steps. Step (1) is to use a solvent (preferably polar compound-13- (11) (11) 200415155, please refer to the following) when a sufficient amount of organic alkali metal initiator RM is present to initiate the polymerization reaction and reach the desired molecular weight. And monovinyl substituted aromatic monomer (sm) are introduced into the reactor to form the first block species RS ^ M. Molecular weight is controlled by on-line or laboratory gel permeation chromatography (GPPC). The weight ratio of s] to the total monomer feed is between 5% and 30%, with 10% to 25% (inclusive) being the best. At the beginning of this step, in the presence of a solvent and an organolithium initiator, the temperature of the monovinyl-substituted aromatic monomer (referred to as the initiation temperature Tinit) is preferably set below 60 ° C, and below 55 ° C, good. The contact time of step (1) is sufficient to allow polymerization to occur until substantially all monomers have been consumed. The completion of the polymerization can be tracked by temperature (high temperature) or on-line spectroscopy. In order to improve the initiation and propagation rate, especially when using alkyl lithium (such as: n-butyl lithium), a small amount of polar compounds can be added, and the mixture of polar compounds and solvents is added to the reaction medium before the initiator is added. By modifying the polarity of the medium, it is possible to 'influence the irregular distribution of monovinyl-substituted aromatic monomers during the copolymerization reaction of the monomer and the conjugated diene in the mixture. Step (2) is the step (1 ) The active cementing material obtained afterwards is introduced into the conjugated diene monomer (B 0. The weight ratio of B ι to the total monomer feed is preferably between 2% and 20%, and between 5% and 15% is the best. The contact time in step (2) is sufficient to allow the reaction to occur until substantially all the monomers are consumed. Step (3) is the introduction of a polyfunctional passivating agent X after the completion of step (2). This passivating agent known in the art is a coupling agent, but is used here for different purposes, which is partially eliminated or passivated. Hereinafter, it is called a passivating agent or a coupling agent (there is no difference between them). Choose this multifunctional The amount of r of the passive passivating agent is as low as (12) (12) 200415155 relative to the actual initiation dose (RMa) of the initiation polymerization ratio. One of the keys to the present invention is to control the individual passivation agent of the initiator The amount of r is adjusted according to the molar amount of active initiator RM a so that the active polymer chain is only Is deactivated. For example, only 60% of the active polymer chain is deactivated by a polyfunctional deactivator. The polyfunctional deactivator X basically has n functionalities (n is from 2 to 8, preferably greater than 2). η can passivate η active polymer species, and a passivating agent is added to the reaction medium. According to one of the key points of the present invention, the addition amount depends on the active initiating dose. Φ In the present invention, the passivating agent X: an initiator (such as: RMa ) The stoichiometric ratio is between 0.5 and 0.9, and preferably between 0.6 and 0.8. This ratio and the molar amount of the polyfunctional passivating agent and active initiator introduced can control the short chain. / Long chain ratio and their individual molecular weights. Suitable passivating agents are the coupling agents listed in columns 3 and 4 of US-P-5,5 4 5,6 9 0. Examples are di- or polyvinyl aromatic compounds, di Or polyketones, di- or polyhalides (preferably silicon halides or halosilanes), esters of monoalcohols and polycarboxylic acids, and mixtures of two or more compounds. Preferred types are epoxidized plant oils (E.g., epoxidized soybean oil, epoxidized castor oil, etc.) or mixtures thereof (e.g., Flexol Plas ticizer LOE (DOW) or Edenol B316 (Henkel) or Vikoflex® (Dow)) 〇 Step (4) is the introduction of a mixture of conjugated flame (B 2) and a monovinyl-substituted aromatic (S2). This The reaction is usually carried out in the presence of an irregular agent or an irregular distribution agent. The irregular distribution agent is introduced into a solvent present in the reaction medium, and the -15- (13) (13) 200415155 is guaranteed in the B2 / s2 segment. The monomers are irregularly distributed. This irregularly distributed agent is a polar compound selected from Lewis bases (such as tertiary amines) and polar agents (including ethers (including cyclic ethers, aliphatic monoethers, and aliphatic polyethers)) . Other agents include, for example: triethylamine, tripropylamine, tributylamine, N-dimethylaniline, tetramethylethylenediamine, pyridine, quinoline and trimethylethylenediamine (this is a tertiary amine example). Examples of ethers of such agents may include tetrahydrofuran, C2 and C3 dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, anisole, dioxin j: end, 1 , 2-dimethoxyethane and tetrahydropyran. The amount of the irregular distribution agent (especially the polar agent) may be 0 · 0 1 to 5 parts / 100 parts by weight of the resin (phi ·). Appropriate selection of a polar compound or an irregular agent 'can adjust the proportion of the irregularly monosubstituted vinyl monomers dispersed in the conjugated diene phase. These polar compounds also affect the 1, 2 addition reaction of the conjugated diene monomer and the resulting vinyl characteristics, so the molecular structure of the Bl-B2 / S2 portion of the copolymer can be adjusted. In one embodiment of the present invention, it may be convenient to add additional amounts of irregularities or polar compounds or mixtures thereof to increase the irregularity of monovinyl-substituted aromatic monomers and / or promote conjugated monoenes. [], 2 _ addition reaction. A weight ratio of S 2 to the total monomer feed is between 50% and 80% 'and is best between 55% and 70%. The weight ratio between I and the total monomer feed is between 5% and 25%, and between 7% and 20%. At the beginning of this step (4), the temperature of the reaction medium (copolymerization reaction temperature,
Tcop。）以低於5(TC爲佳，低於45°C較佳。 -16 - (14) (14)200415155 步驟（4)的接觸時間足以使得聚合反應發生至基本上 所有單體耗盡。聚合反應完成之後，記錄溫度直到突然出 現高溫或利用連線光譜儀。該步驟（4)的溫度高峰以低於 1 2 0 °C爲佳，低於1 1 〇 °c較佳。 聚合反應完全之後，單官能性鈍化劑或終結劑加至反 應器中’以催毀所有殘留的活性聚合鏈。此終結劑可以選 自此技術習知者，如：水、有機酸、醇之類。 終結反應完全之後，基本上滌除反應器的氣體，以濃 縮反應溶液，所得物以提供質子的化合物（此技術已知者） 處理’以移除結合於聚合物種的殘留鹼金屬（若有的話）及 中和存在於反應介質中的任何強鹼。本發明中可選擇之適 當之提供質子的分子包括無機或有機酸、.實例可見於 Lanza 等人的 U . S . P at. N〇 ·4，8 7 7，8 6 3。 最終的去揮發之後或之前，根據此技術已知計技巧， 添加抗氧化劑、抗結塊劑和/或其他技術添加物。 共聚物之用途 根據本發明之方法得到的嵌段共聚物完全透明，且可 以與其他聚合物混合，並用於各式各樣應用。此聚合物包 括，例如，樹脂（如：晶狀聚苯乙烯）、聚烯烴（如：聚乙 烯或聚丙烯）、苯乙烯共聚物（如：苯乙烯一異丁烯酸甲酯 (SMMA)、苯乙烯—馬來酸酐（SMA)、苯乙烯一丙烯腈 (S AN)，可用以藉壓出、熱成型、注射模塑、吹塑或製成 月吴或片製造各式各樣的不同物種。 -17- (15) (15)200415155 耐衝擊I生較咼的透明嵌段共聚物之產製提供選定衝擊 效能、（具類似或經改良透光度）的優點，須減低材料厚度 ’使得材料成本較低且產製速率提高。或者，就相同材料 厚度而盲，所須透光性和耐衝擊性與已知樹脂相仿。 參考下列非限制例地說明本發明之較佳實施例。 分子量Tcop. ) Is less than 5 (TC is preferred, and preferably less than 45 ° C. -16-(14) (14) 200415155 The contact time of step (4) is sufficient to cause the polymerization reaction to occur until substantially all the monomers are consumed. Polymerization After the reaction is completed, record the temperature until a sudden high temperature occurs or use a connected spectrometer. The temperature peak of step (4) is preferably below 120 ° C, and preferably below 110 ° C. After the polymerization reaction is complete, A monofunctional passivator or terminator is added to the reactor to destroy all remaining living polymer chains. This terminator can be selected from those skilled in the art, such as: water, organic acids, alcohols, etc. The termination reaction is complete After that, the reactor gas is substantially purged to concentrate the reaction solution, and the resultant is treated with a compound that provides protons (known in the art) to remove the residual alkali metal (if any) bound to the polymer species and And any strong base present in the reaction medium. Suitable proton-donating molecules that can be selected in the present invention include inorganic or organic acids. Examples can be found in U.S.P. at No. 4,8 of Lanza et al. 7 7, 8 6 3. After the final devolatilization Or before, add antioxidants, anticaking agents, and / or other technical additives according to the known techniques of this technology. Uses of the copolymer The block copolymer obtained according to the method of the present invention is completely transparent and can be polymerized with other It is used in a wide variety of applications. This polymer includes, for example, resins (such as crystalline polystyrene), polyolefins (such as polyethylene or polypropylene), and styrene copolymers (such as: styrene). Monomethyl methacrylate (SMMA), styrene-maleic anhydride (SMA), styrene-acrylonitrile (S AN), can be used for extrusion, thermoforming, injection molding, blow molding, or to make Yue Wu or Manufacture of a variety of different species of tablets. -17- (15) (15) 200415155 The production of transparent block copolymers with high impact resistance and high resistance provides selected impact performance (with similar or improved light transmission) The advantages are that the material thickness must be reduced, so that the material cost is lower and the production rate is increased. Or, blinding for the same material thickness, the required light transmission and impact resistance are similar to known resins. Refer to the following non-limiting examples to explain Preferred implementation of the invention Molecular weight
以尺寸排斥層析法（s E C )測定聚合物分子量。聚合物 先溶解於四氫呋喃（THF)中，注入串聯的2管柱PL-凝膠 <<混合的B>>(1 〇微米/ 30公分）。THF作爲移動相，流 率lml/min。sEC以聚苯乙烯標準品TSK PS(日本TOSOH 產:品）校正。於分佈高峰及組成物關係計算得得到分子量 [實例] 測試程序 組成和無規指數The molecular weight of the polymer was determined by size exclusion chromatography (s E C). The polymer was first dissolved in tetrahydrofuran (THF) and injected into a two-column PL-gel < < Mixed B > > (10 micrometers / 30 cm) in series. THF was used as the mobile phase and the flow rate was 1 ml / min. sEC is calibrated with polystyrene standard TSK PS (made by TOSOH, Japan). The molecular weight is calculated from the distribution peak and the composition relationship. [Example] Test procedure Composition and random index
記錄共聚物溶解於CDCh中之溶液（以三甲基砂院 (TMS)作爲標準品，Oppm)的】H NMR光譜（Brucker DPX 3 00 MHz光譜儀），以測得組成（苯乙烯和丁二：t：希含量）和無 規指數。 於溶液中之黏度 根據ASTM D-4 4 5，測定聚合物於甲本中之丨谷液 -18- (16) (16)200415155 (3 . 8 g於 8 0 m 1中）於 2 5 °C在經校正的毛細管（C a η η ο η -Fens ke)中流動所須時間，測得於溶液中之黏度。之後轉 換成c S t。 熔流率 根據 ASTM D- 1 2 3 8 (2 0 (TC，5kg)測定熔流指數，並 以g / 1 0 m i η表示。 旋流率 測定所謂旋流率而定出樹脂的可注射性。其基於在經 控制的壓力和溫度條件下，樹脂流動通過截面積固定（直 徑4 6mm，長1 2 0 m m，厚2 · 5 m nr)的旋轉道的距離。旋流率 以 cm表示。 條件： 壓力：1 0 0巴 溫度：2 2 0 °C 維持時間：5秒鐘 維持壓力：1 〇 〇巴 模具溫度：3 0 °C 冷卻時間：2 0秒鐘 注射：1 8 0立方公分/秒 耐衝擊性 -19- (17) (17)200415155 根據 ISO 6603 -2 於模製盤（直徑：60mm，厚： 2 mm)上測定耐衝擊性（破裂時肯g量）。 模量和拉伸率 根據 I S 0 1 7 8測定模量。拉伸率係根據z s 〇 5 2 7 - 2 測得。 光學性質 根據 ASTM D-1003 於模製盤（直徑：60mm，厚： 2mm)上測定光學性質。 實例1 : 下列量引至攪拌的加壓反應器中。首先，引入 4 5 6 3 lg溶劑混合物（包含85 %環己烷和15%己院）。之後， 添加9 ·〗2 g四氫呋喃（T H F )和1 5 4 1 g苯乙烯單體（稱爲苯乙 烯1 )。混合物溫度提高至4 5 °C，〇 . 2 5 3莫耳正丁基鋰（於 正己烷中稀釋至20%)迅速注入反應器中。藉此聚合的嵌 段S】分子量是8 6 0 0道耳吞。此第一階段終了時，溫度是 5 4〇C。 之後注入1 260g 1;3-丁二烯（稱爲丁二烯！）以持續後 糸買聚合民應。此弟一個肷段的聚合反應持續3 0 m i η，添加 9g FLEXOL LOE，得到結構（i) R - ( S ] - B 】）X。R - ( S 】-B 】）X 分子量是5 9 6 0 0道耳吞，此第一階段終了時，溫度是5 ；[ °C 。 -20- (18) (18)200415155 同時注入1260g 1,3 -丁二烯（稱爲丁二烯2)和7939g 苯乙烯（稱爲苯乙烯2)地進行反應，以形成R-Sj-B!-B2/S2_M嵌段共聚物，其最終分子量是1566〇〇道耳呑。 此階段期間內，反應介質溫度自4 4 °C升高至9 5 °C。 藉此形成的最終活性聚合物以水鈍化，之後引入有機 酸以中和驗殘餘物。最後，添加Irganox 1076(24.0g)、Record the H NMR spectrum (Brucker DPX 3 00 MHz spectrometer) of the solution of the copolymer dissolved in CDCh (with Trimethyl Sand Institute (TMS) as standard, Oppm) to determine the composition (styrene and succinyl: t: Greek content) and random index. Viscosity in solution According to ASTM D-4 45, determine the polymer in the book 谷 valley solution-18- (16) (16) 200415155 (3.8 g in 80 m 1) at 2 5 ° The time required for C to flow in a calibrated capillary (C a η η ο η -Fens ke). Measure the viscosity in solution. It is then converted to c S t. Melt flow rate The melt flow index was measured in accordance with ASTM D- 1 2 3 8 (2 0 (TC, 5 kg) and expressed as g / 10 mi η. The swirl rate was measured to determine the so-called swirl rate to determine the injectability of the resin. It is based on the distance under which the resin flows through a rotating track with a fixed cross-sectional area (diameter 46 mm, length 120 mm, thickness 2.5 mm nr) under controlled pressure and temperature conditions. The swirl rate is expressed in cm. Conditions: Pressure: 100 bar Temperature: 220 ° C Hold time: 5 seconds Hold pressure: 1000 bar Mold temperature: 30 ° C Cooling time: 20 seconds Injection: 180 cm3 / Impact resistance per second -19- (17) (17) 200415155 The impact resistance (amount of Ken g at break) was measured on a molded disc (diameter: 60 mm, thickness: 2 mm) according to ISO 6603 -2. Modulus and pull The elongation is measured according to IS 0 1 7 8. The elongation is measured according to zs 〇 5 2 7-2. Optical properties According to ASTM D-1003, the optics are measured on a molding disc (diameter: 60mm, thickness: 2mm). Example 1. The following quantities were introduced into a stirred pressure reactor. First, 4 5 6 3 lg of a solvent mixture (containing 85% cyclohexane and 15% hexane) was introduced. After that, 9 · 2 g of tetrahydrofuran (THF) and 151 1 g of styrene monomer (called styrene 1) were added. The temperature of the mixture was increased to 4 5 ° C, 0.2 5 3 mole n-butyl Lithium (diluted to 20% in n-hexane) was quickly injected into the reactor. The molecular weight of the polymerized block S] was 8600 channels. At the end of this first stage, the temperature was 5400C. After that Inject 1 260g of 1; 3-butadiene (known as butadiene!) To continue to polymerize the polymer. The polymerization reaction of this unit lasts 30 mi η, and 9g of FLEXOL LOE is added to obtain the structure (i ) R-(S]-B)) X. R-(S) -B)) X molecular weight is 5 9 6 0 ear puffs. At the end of this first stage, the temperature is 5; [° C. -20 -(18) (18) 200415155 Simultaneously inject 1260 g of 1,3-butadiene (called butadiene 2) and 7939 g of styrene (called styrene 2) to react to form R-Sj-B!- The final molecular weight of the B2 / S2_M block copolymer is 156,000 ohms. During this phase, the temperature of the reaction medium increases from 44 ° C to 95 ° C. The final living polymer formed by this is water Passivation followed by introduction of organic Acid to neutralize the residue. Finally, add Irganox 1076 (24.0g),
Irgaonx 3 05 2( 1 2.0g)和 TNPP(84.0g)形成的抗氧化劑系統 。移除溶劑地回收此共聚物並造粒。 實例1之共聚物特性： 苯乙烯含量：79.6% 1，3-丁二烯含量：20.4% 無規苯乙烯：1 7 . 1 % 熔流指數·· 1 4g/l Omin 於溶液中之黏度：5.0c St 實例1之共聚物評估： ® 旋流率：06cm i 彎曲模量：1 3 7 3 Μ P a 破裂時拉伸率：1 9 2 % 濁度：1 . 3 % 破裂時能量：29焦耳 柔軟 亦注射實例1之共聚物，以得到一般物件（如：影像 -21 - (19) (19)200415155 帶或6 00微米杯）。此物件具高品質和良好模製塑性。 實例2 重覆實例1，除下列者以外，所有條件常數相同： 苯乙嫌1 : 1 5 6 0 g 丁二烯 1 : 1 2 0 0 g 苯乙烯2: 7440g 丁二烯 2 : 1 8 0 0 g • 實例2之共聚物特性 苯乙烯含量：74.9% ..1，3-丁二烯含量：2^1% R-( Si分子量：7 1 0 00克/莫耳 R-S】-B】-B2/S2-M分子量：1 5 9000克/莫耳 無規苯乙烯：1 7 . 1 % 熔流指數：1 5 g/1 OminAn antioxidant system formed by Irgaonx 3 05 2 (1 2.0g) and TNPP (84.0g). The copolymer was recovered with the solvent removed and pelletized. Copolymer characteristics of Example 1: Styrene content: 79.6% 1,3-butadiene content: 20.4% Random styrene: 17.1% Melt flow index ·· 1 4g / l Omin Viscosity in solution: Evaluation of the copolymer of 5.0c St Example 1: ® Swirl rate: 06 cm i Flexural modulus: 1 3 7 3 MPa Elongation at break: 19 2% Turbidity: 1.3% Energy at break: 29 Joule softness was also injected with the copolymer of Example 1 to obtain a general object (eg, image-21-(19) (19) 200415155 tape or 600 micron cup). This object has high quality and good molding plasticity. Example 2 Example 1 is repeated, except for the following, all condition constants are the same: styrene 1: 1 5 6 0 g butadiene 1: 1 2 0 0 g styrene 2: 7440 g butadiene 2: 1 8 0 0 g • Characteristics of the copolymer of Example 2 Styrene content: 74.9% .. 1,3-butadiene content: 2 ^ 1% R- (Si molecular weight: 7 1 0 00 g / mol RS] -B]- B2 / S2-M Molecular weight: 1 5 9000 g / mole random styrene: 17.1% Melt flow index: 1 5 g / 1 Omin
實例2之共聚物評估： 旋流率：6 7 c m 彎曲模量：1230MPa 破裂時拉伸率：2 0 8 % 濁度：2.5 % 破裂時能量：27焦耳 柔軟 -22 - (20) (20)200415155 比較例3 下列量引至攪拌的加壓反應器中。首先，引入 44 1 93 g溶劑混合物（包含85%環己烷和15%己烷）。之後， 添加9.63g四氫呋喃（THF)和20 0 0g苯乙烯單體（稱爲苯乙 烯1)。混合物溫度提高至45 °C，0.170莫耳正丁基鋰（於 正己烷中稀釋至20%)迅速注入反應器中。藉此聚合的嵌 段S!分子量是1 6 8 00道耳吞。此第一階段終了時，溫度 是 54°C。 之後注入3 240g 1，3-丁二烯（稱爲丁二烯1)和6760g β 苯乙烯（稱爲苯乙烯2)以進行聚合反應，形成R-Si-Bi/Sr Μ嵌段共聚物，其最終分子量是1 0 8 6 0 0道耳呑。此階段 期間內，·反應介質溫度自45 °C升高至95 °C。 藉此形成的最終活性聚合物以水鈍化，之後引入丙酸 以中和鹼殘餘物。最後，添加 Irganox 1 076(24.0g)、Evaluation of the copolymer of Example 2: Swirl rate: 67 cm Flexural modulus: 1230 MPa Elongation at break: 2.08% Turbidity: 2.5% Energy at break: 27 Joules -22-(20) (20) 200415155 Comparative Example 3 The following amount was introduced into a stirred pressure reactor. First, 44 1 93 g of a solvent mixture (containing 85% cyclohexane and 15% hexane) was introduced. Thereafter, 9.63 g of tetrahydrofuran (THF) and 2000 g of a styrene monomer (referred to as styrene 1) were added. The temperature of the mixture was raised to 45 ° C, and 0.170 mol n-butyllithium (diluted to 20% in n-hexane) was quickly injected into the reactor. The molecular weight of the block S! Polymerized by this was 1,680,000 ear swallows. At the end of this first phase, the temperature was 54 ° C. 3 240 g of 1,3-butadiene (called butadiene 1) and 6760 g of beta styrene (called styrene 2) are then injected for polymerization to form an R-Si-Bi / Sr Μ block copolymer, Its final molecular weight is 10,860 ears. During this phase, the temperature of the reaction medium increased from 45 ° C to 95 ° C. The final living polymer thus formed was passivated with water, and then propionic acid was introduced to neutralize the alkali residue. Finally, add Irganox 1 076 (24.0g),
Irgaonχ 3 0 5 2( 1 2.0g)和TNPP(84·0g)形成的抗氧化劑系統 。移除溶劑地回收此共聚物並造粒。 比較例3之共聚物特性： 苯乙烯含量：7 5 · 7 % 1，3 - 丁二烯含量：2 4 · 3 % 無規苯乙烯：1 7 . 1 % 熔流指數：15g/l〇min 於溶液中之黏度：4 · 9 c S t >23- (21) (21)200415155 比較例3之共聚物評估： 旋流率：4 5 c m 彎曲模量：900MPa 破裂時拉伸率：4 7 5 % 濁度：2.6 % 破裂時能量：3 1焦耳 柔軟 雖然實例2和3的共聚物具有相同苯乙烯含量、相同 無規苯乙烯含量和類似熔流率，實例3的共聚物之可注射 性較差。此顯示製備共聚物的中間鈍化步驟顯著改善聚合 物性質。- 下列的附表列出此處所述共聚物所得性質與其他樹脂 之比較。 實例1 實例2 實例3(比較例） 苯乙嫌含量[%] 79.6 74.9 75.7 無規苯乙烯[%] 17.1 17.0 17.1 熔流率[g /1 〇 m i η ] 14 15 1 5 旋流率[cm] 66 67 4 5 彎曲模量[MPa] 13 73 1230 900 破裂時拉伸率[%] 195 208 475 破裂時能量[焦耳] 29 27 6 1 濁度[%] 1.3 2.5 2.6An antioxidant system formed by Irgaonχ 3 0 5 2 (1 2.0g) and TNPP (84 · 0g). The copolymer was recovered with the solvent removed and pelletized. Copolymer characteristics of Comparative Example 3: Styrene content: 7 5 · 7% 1,3-butadiene content: 2 4 · 3% Random styrene: 17.1% Melt flow index: 15 g / 10 min Viscosity in solution: 4 · 9 c S t > 23- (21) (21) 200415155 Evaluation of copolymer of Comparative Example 3: Swirl rate: 4 5 cm Flexural modulus: 900 MPa Elongation at break: 4 75% Turbidity: 2.6% Energy at break: 3 1 Joule is soft Although the copolymers of Examples 2 and 3 have the same styrene content, the same random styrene content, and similar melt flow rates, the copolymer of Example 3 is injectable Poor sex. This shows that the intermediate passivation step to prepare the copolymer significantly improves polymer properties. -The following table lists the properties of the copolymers described here compared to other resins. Example 1 Example 2 Example 3 (comparative example) Styrene content [%] 79.6 74.9 75.7 Random styrene [%] 17.1 17.0 17.1 Melt flow rate [g / 1 〇mi η] 14 15 1 5 Swirl rate [cm ] 66 67 4 5 Flexural modulus [MPa] 13 73 1230 900 Elongation at break [%] 195 208 475 Energy at break [Joule] 29 27 6 1 Turbidity [%] 1.3 2.5 2.6